831 |
|
error of splitting method in terms of commutator of the |
832 |
|
operators(\ref{introEquation:exponentialOperator}) associated with |
833 |
|
the sub-flow. For operators $hX$ and $hY$ which are associate to |
834 |
< |
$\varphi_1(t)$ and $\varphi_2(t$ respectively , we have |
834 |
> |
$\varphi_1(t)$ and $\varphi_2(t)$ respectively , we have |
835 |
|
\begin{equation} |
836 |
|
\exp (hX + hY) = \exp (hZ) |
837 |
|
\end{equation} |
846 |
|
\] |
847 |
|
Applying Baker-Campbell-Hausdorff formula to Sprang splitting, we |
848 |
|
can obtain |
849 |
< |
\begin{eqnarray*} |
849 |
> |
\begin{equation} |
850 |
|
\exp (h X/2)\exp (h Y)\exp (h X/2) & = & \exp (h X + h Y + h^2 |
851 |
|
[X,Y]/4 + h^2 [Y,X]/4 \\ & & \mbox{} + h^2 [X,X]/8 + h^2 [Y,Y]/8 \\ |
852 |
|
& & \mbox{} + h^3 [Y,[Y,X]]/12 - h^3 [X,[X,Y]]/24 & & \mbox{} + |
853 |
|
\ldots ) |
854 |
< |
\end{eqnarray*} |
854 |
> |
\end{equation} |
855 |
|
Since \[ [X,Y] + [Y,X] = 0\] and \[ [X,X] = 0\], the dominant local |
856 |
|
error of Spring splitting is proportional to $h^3$. The same |
857 |
|
procedure can be applied to general splitting, of the form |
892 |
|
simulations. For instance, instantaneous temperature of an |
893 |
|
Hamiltonian system of $N$ particle can be measured by |
894 |
|
\[ |
895 |
< |
T(t) = \sum\limits_{i = 1}^N {\frac{{m_i v_i^2 }}{{fk_B }}} |
895 |
> |
T = \sum\limits_{i = 1}^N {\frac{{m_i v_i^2 }}{{fk_B }}} |
896 |
|
\] |
897 |
|
where $m_i$ and $v_i$ are the mass and velocity of $i$th particle |
898 |
|
respectively, $f$ is the number of degrees of freedom, and $k_B$ is |
913 |
|
These three individual steps will be covered in the following |
914 |
|
sections. Sec.~\ref{introSec:initialSystemSettings} deals with the |
915 |
|
initialization of a simulation. Sec.~\ref{introSec:production} will |
916 |
< |
discusses issues in production run, including the force evaluation |
917 |
< |
and the numerical integration schemes of the equations of motion . |
918 |
< |
Sec.~\ref{introSection:Analysis} provides the theoretical tools for |
919 |
< |
trajectory analysis. |
916 |
> |
discusses issues in production run. Sec.~\ref{introSection:Analysis} |
917 |
> |
provides the theoretical tools for trajectory analysis. |
918 |
|
|
919 |
|
\subsection{\label{introSec:initialSystemSettings}Initialization} |
920 |
|
|
984 |
|
|
985 |
|
\subsection{\label{introSection:production}Production} |
986 |
|
|
987 |
< |
\subsubsection{\label{introSec:forceCalculation}The Force Calculation} |
987 |
> |
Production run is the most important steps of the simulation, in |
988 |
> |
which the equilibrated structure is used as a starting point and the |
989 |
> |
motions of the molecules are collected for later analysis. In order |
990 |
> |
to capture the macroscopic properties of the system, the molecular |
991 |
> |
dynamics simulation must be performed in correct and efficient way. |
992 |
> |
|
993 |
> |
The most expensive part of a molecular dynamics simulation is the |
994 |
> |
calculation of non-bonded forces, such as van der Waals force and |
995 |
> |
Coulombic forces \textit{etc}. For a system of $N$ particles, the |
996 |
> |
complexity of the algorithm for pair-wise interactions is $O(N^2 )$, |
997 |
> |
which making large simulations prohibitive in the absence of any |
998 |
> |
computation saving techniques. |
999 |
|
|
1000 |
< |
\subsubsection{\label{introSection:integrationSchemes} Integration |
1001 |
< |
Schemes} |
1000 |
> |
A natural approach to avoid system size issue is to represent the |
1001 |
> |
bulk behavior by a finite number of the particles. However, this |
1002 |
> |
approach will suffer from the surface effect. To offset this, |
1003 |
> |
\textit{Periodic boundary condition} is developed to simulate bulk |
1004 |
> |
properties with a relatively small number of particles. In this |
1005 |
> |
method, the simulation box is replicated throughout space to form an |
1006 |
> |
infinite lattice. During the simulation, when a particle moves in |
1007 |
> |
the primary cell, its image in other cells move in exactly the same |
1008 |
> |
direction with exactly the same orientation. Thus, as a particle |
1009 |
> |
leaves the primary cell, one of its images will enter through the |
1010 |
> |
opposite face. |
1011 |
> |
%\begin{figure} |
1012 |
> |
%\centering |
1013 |
> |
%\includegraphics[width=\linewidth]{pbcFig.eps} |
1014 |
> |
%\caption[An illustration of periodic boundary conditions]{A 2-D |
1015 |
> |
%illustration of periodic boundary conditions. As one particle leaves |
1016 |
> |
%the right of the simulation box, an image of it enters the left.} |
1017 |
> |
%\label{introFig:pbc} |
1018 |
> |
%\end{figure} |
1019 |
> |
|
1020 |
> |
%cutoff and minimum image convention |
1021 |
> |
Another important technique to improve the efficiency of force |
1022 |
> |
evaluation is to apply cutoff where particles farther than a |
1023 |
> |
predetermined distance, are not included in the calculation |
1024 |
> |
\cite{Frenkel1996}. The use of a cutoff radius will cause a |
1025 |
> |
discontinuity in the potential energy curve |
1026 |
> |
(Fig.~\ref{introFig:shiftPot}). Fortunately, one can shift the |
1027 |
> |
potential to ensure the potential curve go smoothly to zero at the |
1028 |
> |
cutoff radius. Cutoff strategy works pretty well for Lennard-Jones |
1029 |
> |
interaction because of its short range nature. However, simply |
1030 |
> |
truncating the electrostatic interaction with the use of cutoff has |
1031 |
> |
been shown to lead to severe artifacts in simulations. Ewald |
1032 |
> |
summation, in which the slowly conditionally convergent Coulomb |
1033 |
> |
potential is transformed into direct and reciprocal sums with rapid |
1034 |
> |
and absolute convergence, has proved to minimize the periodicity |
1035 |
> |
artifacts in liquid simulations. Taking the advantages of the fast |
1036 |
> |
Fourier transform (FFT) for calculating discrete Fourier transforms, |
1037 |
> |
the particle mesh-based methods are accelerated from $O(N^{3/2})$ to |
1038 |
> |
$O(N logN)$. An alternative approach is \emph{fast multipole |
1039 |
> |
method}, which treats Coulombic interaction exactly at short range, |
1040 |
> |
and approximate the potential at long range through multipolar |
1041 |
> |
expansion. In spite of their wide acceptances at the molecular |
1042 |
> |
simulation community, these two methods are hard to be implemented |
1043 |
> |
correctly and efficiently. Instead, we use a damped and |
1044 |
> |
charge-neutralized Coulomb potential method developed by Wolf and |
1045 |
> |
his coworkers. The shifted Coulomb potential for particle $i$ and |
1046 |
> |
particle $j$ at distance $r_{rj}$ is given by: |
1047 |
> |
\begin{equation} |
1048 |
> |
V(r_{ij})= \frac{q_i q_j \textrm{erfc}(\alpha |
1049 |
> |
r_{ij})}{r_{ij}}-\lim_{r_{ij}\rightarrow |
1050 |
> |
R_\textrm{c}}\left\{\frac{q_iq_j \textrm{erfc}(\alpha |
1051 |
> |
r_{ij})}{r_{ij}}\right\}. \label{introEquation:shiftedCoulomb} |
1052 |
> |
\end{equation} |
1053 |
> |
where $\alpha$ is the convergence parameter. Due to the lack of |
1054 |
> |
inherent periodicity and rapid convergence,this method is extremely |
1055 |
> |
efficient and easy to implement. |
1056 |
> |
%\begin{figure} |
1057 |
> |
%\centering |
1058 |
> |
%\includegraphics[width=\linewidth]{pbcFig.eps} |
1059 |
> |
%\caption[An illustration of shifted Coulomb potential]{An illustration of shifted Coulomb potential.} |
1060 |
> |
%\label{introFigure:shiftedCoulomb} |
1061 |
> |
%\end{figure} |
1062 |
|
|
1063 |
+ |
%multiple time step |
1064 |
+ |
|
1065 |
|
\subsection{\label{introSection:Analysis} Analysis} |
1066 |
|
|
1067 |
|
Recently, advanced visualization technique are widely applied to |
1076 |
|
|
1077 |
|
\subsubsection{\label{introSection:thermodynamicsProperties}Thermodynamics Properties} |
1078 |
|
|
1079 |
+ |
Thermodynamics properties, which can be expressed in terms of some |
1080 |
+ |
function of the coordinates and momenta of all particles in the |
1081 |
+ |
system, can be directly computed from molecular dynamics. The usual |
1082 |
+ |
way to measure the pressure is based on virial theorem of Clausius |
1083 |
+ |
which states that the virial is equal to $-3Nk_BT$. For a system |
1084 |
+ |
with forces between particles, the total virial, $W$, contains the |
1085 |
+ |
contribution from external pressure and interaction between the |
1086 |
+ |
particles: |
1087 |
+ |
\[ |
1088 |
+ |
W = - 3PV + \left\langle {\sum\limits_{i < j} {r{}_{ij} \cdot |
1089 |
+ |
f_{ij} } } \right\rangle |
1090 |
+ |
\] |
1091 |
+ |
where $f_{ij}$ is the force between particle $i$ and $j$ at a |
1092 |
+ |
distance $r_{ij}$. Thus, the expression for the pressure is given |
1093 |
+ |
by: |
1094 |
+ |
\begin{equation} |
1095 |
+ |
P = \frac{{Nk_B T}}{V} - \frac{1}{{3V}}\left\langle {\sum\limits_{i |
1096 |
+ |
< j} {r{}_{ij} \cdot f_{ij} } } \right\rangle |
1097 |
+ |
\end{equation} |
1098 |
+ |
|
1099 |
|
\subsubsection{\label{introSection:structuralProperties}Structural Properties} |
1100 |
|
|
1101 |
|
Structural Properties of a simple fluid can be described by a set of |
1102 |
|
distribution functions. Among these functions,\emph{pair |
1103 |
|
distribution function}, also known as \emph{radial distribution |
1104 |
< |
function}, are of most fundamental importance to liquid-state |
1105 |
< |
theory. Pair distribution function can be gathered by Fourier |
1106 |
< |
transforming raw data from a series of neutron diffraction |
1107 |
< |
experiments and integrating over the surface factor \cite{Powles73}. |
1108 |
< |
The experiment result can serve as a criterion to justify the |
1109 |
< |
correctness of the theory. Moreover, various equilibrium |
1110 |
< |
thermodynamic and structural properties can also be expressed in |
1111 |
< |
terms of radial distribution function \cite{allen87:csl}. |
1104 |
> |
function}, is of most fundamental importance to liquid-state theory. |
1105 |
> |
Pair distribution function can be gathered by Fourier transforming |
1106 |
> |
raw data from a series of neutron diffraction experiments and |
1107 |
> |
integrating over the surface factor \cite{Powles73}. The experiment |
1108 |
> |
result can serve as a criterion to justify the correctness of the |
1109 |
> |
theory. Moreover, various equilibrium thermodynamic and structural |
1110 |
> |
properties can also be expressed in terms of radial distribution |
1111 |
> |
function \cite{allen87:csl}. |
1112 |
|
|
1113 |
|
A pair distribution functions $g(r)$ gives the probability that a |
1114 |
|
particle $i$ will be located at a distance $r$ from a another |
1150 |
|
function is called \emph{auto correlation function}. One example of |
1151 |
|
auto correlation function is velocity auto-correlation function |
1152 |
|
which is directly related to transport properties of molecular |
1153 |
< |
liquids. Another example is the calculation of the IR spectrum |
1154 |
< |
through a Fourier transform of the dipole autocorrelation function. |
1153 |
> |
liquids: |
1154 |
> |
\[ |
1155 |
> |
D = \frac{1}{3}\int\limits_0^\infty {\left\langle {v(t) \cdot v(0)} |
1156 |
> |
\right\rangle } dt |
1157 |
> |
\] |
1158 |
> |
where $D$ is diffusion constant. Unlike velocity autocorrelation |
1159 |
> |
function which is averaging over time origins and over all the |
1160 |
> |
atoms, dipole autocorrelation are calculated for the entire system. |
1161 |
> |
The dipole autocorrelation function is given by: |
1162 |
> |
\[ |
1163 |
> |
c_{dipole} = \left\langle {u_{tot} (t) \cdot u_{tot} (t)} |
1164 |
> |
\right\rangle |
1165 |
> |
\] |
1166 |
> |
Here $u_{tot}$ is the net dipole of the entire system and is given |
1167 |
> |
by |
1168 |
> |
\[ |
1169 |
> |
u_{tot} (t) = \sum\limits_i {u_i (t)} |
1170 |
> |
\] |
1171 |
> |
In principle, many time correlation functions can be related with |
1172 |
> |
Fourier transforms of the infrared, Raman, and inelastic neutron |
1173 |
> |
scattering spectra of molecular liquids. In practice, one can |
1174 |
> |
extract the IR spectrum from the intensity of dipole fluctuation at |
1175 |
> |
each frequency using the following relationship: |
1176 |
> |
\[ |
1177 |
> |
\hat c_{dipole} (v) = \int_{ - \infty }^\infty {c_{dipole} (t)e^{ - |
1178 |
> |
i2\pi vt} dt} |
1179 |
> |
\] |
1180 |
|
|
1181 |
|
\section{\label{introSection:rigidBody}Dynamics of Rigid Bodies} |
1182 |
|
|
1238 |
|
where $I_{ii}$ is the diagonal element of the inertia tensor. This |
1239 |
|
constrained Hamiltonian equation subjects to a holonomic constraint, |
1240 |
|
\begin{equation} |
1241 |
< |
Q^T Q = 1$, \label{introEquation:orthogonalConstraint} |
1241 |
> |
Q^T Q = 1, \label{introEquation:orthogonalConstraint} |
1242 |
|
\end{equation} |
1243 |
|
which is used to ensure rotation matrix's orthogonality. |
1244 |
|
Differentiating \ref{introEquation:orthogonalConstraint} and using |